Three-phase aerosol spraying systems



United States Patent O 3,547,854 THREE-PHASE AEROSOL SPRAYING SYSTEMSWilly Roth, Strengelbach, Aargau, and Otto Erwin Schenk,

Basel, Switzerland, assignors to Geigy Chemical Corporation, Ardsley,N.Y., a corporation of New York No Drawing. Continuation-impart ofapplication Ser. No. 391,800, Aug. 24, 1964, which is acontinuation-in-part of application Ser. No. 267,771, Mar. 25, 1963.This application Aug. 21, 1967, Ser. No. 661,835 Claims priority,application Switzerland, Mar. 30, 1962, 3,864/ 62 Int. Cl. C08f /34;C08b 27/42; C08k ]/32 US. Cl. 26029.6 13 Claims ABSTRACT OF THEDISCLOSURE In three-phase aerosol spraying systems comprising, in anaerosol pressure vessel, an aqueous phase to be sprayed which containsas active substance a textile finishing agent, a liquefied organicpropellant phase, and the gas phase of the propellant, the improvementof avoiding excessive foam formation and obtaining optimal spraydistribution in the sprayed-on zone on the substrate, by providing inthe system a lipophilic interface active agent of an HLB value ofmaximally 6 which is a water-insoluble monoor di-lower alkyl ether ofmonoethylene glycol or diethylene glycol and has at least 6 and not morethan 12 carbon atoms per molecule; thereby, formation of a foam-causingtype emulsion of the liquefied propellant and aqueous phase is avoided,which type of emulsion is usually undesirable in spraying textilefinishing agents, and foam formation is suppressed.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of my pending patent application Ser. No. 391,800,filed Aug. 24, 1964 and now abandoned, which is in turn acontinuationin-part of my abandoned patent application, Ser. No.267,771, filed Mar. 25, 1963.

DESCRIPTION OF THE INVENTION other conventional types of aerosolsconsisting in that the liquefied propellant cannot be mixed with theliquid phase to be sprayed. The three phases of such three-phaseaerosols are the following:

(1) The aqueous phase to be sprayed, wherein active substances aredispersed, e.g. dissolved, suspended or emulsified,

(2) The liquefied propellant, and

(3) The gas phase of the propellant.

The liquefied propellant is disposed either above or below the aqueousphase to be sprayed according to its specific Weight, the phases notbeing emulsified, but separated from each other and forming an interfacebetween them, and the gas phase of the propellant is disposed in eachcase above the two liquid phases. For some purposes, formation of awater-in-oil emulsion has been recommended. For the purposes of theinstant invention, this should be avoided.

It is known that normally a very fine spray of water can only beattained when high pressures are applied (of above 10 atm. gauge) withthe aid of special spray nozzles, whereas for commercial spray nozzlesgenerally pressures 'ice of up to 5 atm. gauge are used. Consequentlythe fine spraying of the purely aqueous phase of a three phase aerosolis far from perfect even when so-called rotatory nozzles are used.

For improving the sprayability of the water or the aqueous phase ofthree-phase aerosols, it has hitherto been necessary to addwater-soluble organic liquids, especially mono-hydric lower alkanols, inhigh quantities. Thus, in three-phase aerosols mixtures of ethanol orisopropanol and Water are normally sprayed, the alcohol content of whichaqueous mixtures may amount to as high as The use of ethanol or the likelower alkanols in the aqueous phase, While mainly intended to improvesprayability, also serves to facilitate dissolution of organic activesubstances in the aqueous phase; however, this use has the disadvantagethat such systems are more expensive and are more dangerous on accountof the combustibility of the organic components. A further decisivedisadvantage of the use of water-miscible organic liquids, such as theaforesaid alcohols, in the aqueous phase to be sprayed, of a three phaseaerosol, consists in that these adjuvants have a flocculating action onaqueous colloidal disperse systems. For example, an aqueous starchsolution, which is a principal textile finishing agent is coagulated dueto the addition of ethanol, and the known device of the addition ofwater-soluble organic solvents for the improvement of the sprayabilityof such a system completely fails in this instance. If an improvement ofthe sprayability of the aqueous phase is attempted by adding normalwetting agents for the purpose of reducing the surface tension, then afairly substantial intimate intermingling of the liquid aqueous andorganic phases occurs in the threephase aerosols on account of thereduced surface tension, and this leads to an undesired foam formationwhen the aerosol valve is actuated. Three-phase aerosols, to whichconventional wetting agents have been added, cannot be used for mostpractical purposes on account of this foam formation.

The improved novel system according to the invention contains, in aconventional pressure vessel having a spray valve, a sprayable mixturewhich consists essentially of an aqueous phase to be sprayed, aliquefied organic propellant phase and the gas phase of the propellant,and the inventive improvement consists more particularly in that saidsprayable mixture, contained in the vessel in which said aqueous phaseand said liquid propellant are separated from each other forming acommon interface between them, i.e. they are not emulsified with eachother, is substantially free from monohydric alkanols, and containsabove 50% by weight of water, and, as a spray improving agent, alipophilic interface active agent having an HLB-value according toGriflin of maximally 6 and defined more in detail below, whereby themajor portion of said lipophilic interface-active agent is present insaid liquefied propellant phase and a minor portion in said aqueousphase, foam causing emulsions are avoided and foam formation issuppressed. This agent is preferably a single lipophilic organiccompound but may also be a mixture of different substances.

According to Griflin [see W. C. Griffin, Journal of Soc. Cosm. Chemists,vol. 1, 311, (1949) and vol. 5, 249, (1954)] and an article inParfiimerie und Kosmetik, vol. 41, (1960), each interface active dipolarsubstance is correlated with a numerical value in an arbitrarilyselected scale which runs from these numerical values, the so-called HLBvalues, represent a measure for the degree of the lipophilic orhydrophilic nature of the respective substances; lipophilic substanceshave a low HLB number, whereas substances having an increasinglyhydrophilic character always have higher HLB values. The boundary valuebetween lipophilic and hydrophilic" is approximately at the HLB number 310. As stated above, in the mixtures according to the invention,substances having an HLB value of 1 to 6 are concentrated in the liquidorganic propellant phase on account of their pronounced lipophiliccharacter, whereas they are contained in the aqueous phase to be sprayedin a very small concentration; this distribution is advantageous whensensitive disperse systems are present in the aqueous phase to besprayed.

A rapid determination of the HLB value of interfaceactive substances maybe made on the basis of the behaviour towards Water. Substances havingan HLB value of up to 6 are those water-soluble surface-active compoundswhich cannot or can only be sparingly dispersed when shaken with waterand do not give a milky dispersion even after vigorous shaking. Thismethod of determining HLB values of surface-active substances of themost varied classes of compounds is known from the literature alreadycited and in particular from Parf'timerie und Kosmetik, volume 41,(1960), page 86.

Interface-active substances having an HLB value of up to 6, which areparticularly suitable for use in the mixture according to the inventionas spray improving interface-active agents, are monoand diethers ofglycols with alcohols, preferably alkanols of 4 to 6 carbon atoms, andespecially the mono-alkyl and di-alkyl ethers of ethylene glycol anddiethyleneglycol having a total of at least 6 and preferably not morethan 12 carbon atoms, for example, ethyleneglycol mono-n-hexyl ether,diethyleneglycol mono-n-hexyl ether, ethyleneglycol di-n-butyl ether,

diethyleneglycol di-n-butyl ether, propyleneglycol monobutyl ether, etc.Allyl in the most preferred class of these ethers has also from 4 to 6carbon atoms.

The mixture in the system according to the invention contains as activesubstance, dissolved or dispersed in the aqueous phase to be sprayed,finishing agents for textiles, because on the one hand the lipophilicinterfaceactive substances having an HLB value of 6 at the miximumconsiderably facilitate the hot pressing of the textiles treated withthe finishing agent and on the other hand the said spray improvementagents do not exert an adverse effect on the colloidal disperse systemof the finishing agent, and do not cause disturbing foam formation or anexcessively narrow spray angle and irregular spray density on thesprayed-on area of the textile substrate.

The mixture for finishing textiles may be composed, for example, asfollows and may contain the following groups of substances:

(a) Finishing agents: which are dissolved or dispersed in water andwhich, calculated on the total weight of the mixture to be sprayedamount to 0.520% by weight, may belong to the following classes:

natural and modified starches or derivatives thereof, cellulosederivatives,

polyvinylalcohols,

polyvinylacetates,

polystyrene resins,

polyacrylic resins, etc.

(b) Spray improving agent as defined above, in an amount of 0.1-% of thetotal mixture to be sprayed.

(c) Propellants: unhalogenated or halogenated gaseous hydrocarbons ormixtures thereof, which may be liquified under pressure and which have apressure of at least 0.5 atm. gauge at C. and cannot be mixed withwater, for example propane, butane, dichlorodifiuoromethane,dichlorotetrafluoroethane, Propane/butane mixtures, especially of aweight ratio in the range of 10:90 to 40:50 give particularlysatisfactory results.

The required quantity of propellant is based on the physical behaviourof the propellant, the composition of the aqueous phase to be sprayed ofthe mixture according to the invention, the type of valve used and thevolume of the pressure vessel used; the proportion of propellant in themixture generally lies between 2 and The mixture according to theinvention for finishing textiles may also contain the followingauxiliary substances as well as the above substances:

((1) Softening agents: in quantities of 0.5 to 5% of the mixture,preferably polyhydric alcohols, for example ethyleneglycol,propyleneglycol, polyethyleneglycol, polypropyleneglycol, glycerol,etc.,

(e) Optical whitening agents: in quantities of 0.01 to 0.5% of themixture, for example stilbene derivatives, triazole derivatives,benzimidazole derivatives, etc.,

(f) Anti-microbials: in quantities of 0.1 to 5% of the mixture, forexample substituted benzoxazolones, substituted salicyclic acidanilides, substituted phenols, organotin-compounds, halogen isocyanuricacid derivatives, etc.,

(g) Perfumes: in quantities of 0.1 to 1% of the mixture, for exampleessential oils, synthetic perfumes, etc.

The following may be stated on the action of the auxiliary substances:

The softening agents prevent inter alia a blockage of the spray nozzlesby reducing the adhesion and the hardness of the films of the finishingagents forming on drying. The aerosol systems according to theinvention, therefore, preferably contain such softening agents in theabovestated amounts. The presence of softening agents also assists incompletely suppressing foam formation. The optical whitening agentsproduce on white textiles an intense white effect and theanti-microbials prevent inter alia the formation of odour in textilessoaked with perspiration. The perfumes finally give the product apleasant smell which is desirable in application and in the treatedtextiles.

Sprayed from an aerosol bomb equipped with a precision valve having astem orifice of 2 times 0.020" and a mechanical breakup button at anangle of about onto a textile fabric over a distance of 20 cm., a spraycircle of at least about 8 to 12 cm. and with preferred systems of 12 to18 cm. diameter is obtained, free from any disturbing foam formation.

The following non-limitative examples explain some preferred embodimentsof the mixture according to the invention more fully. Parts thereinrepresent parts by weight. The HLB values of the spray improvementagents used are taken from the table on page 89 of the said publicationParf'timerie und Kosmetik.

EXAMPLE 1 Starch derivative soluble in hot water Ethylene glycol dibutylether 1 Propyleneglycol Lavender oil 0.3

Water 72.2

Propane/butane (20:80) 20.0

1 (The formula of this compound is CtHo-OCH2CH2OC4H41 it is commerciallyavailable as dibutylcello solvc).

The hot water soluble starch derivative is dissolved in hot water, theremaining components of the mixture, apart from the propellant, areadded to the starch solution and homogenized in a suitable apparatus.The mixture is treated with propane/butane (20:80) in a pressurecontainer equipped with a precision valve having a stem orifice of 2times 0.020" and a mechanical breakup button. This preparation may bereadily sprayed; sprayed on cotton, it produces after hot pressing anexcellent starch effect.

EXAMPLE 2 Parts Polyvinyl alcohol 1.50 Z-n-hexyloxy-ethanol,commercially 2.00 Available as hexylcellosolve ethyleneglycol 1.00 Thesodium salt of 2-(stilbyl-4")-(naphtho-1',2:4,

5) l.2,3-triaZole-2,6-disulphonic acid 0.05 Orange oil 0.25 Water 92.20lso-butane 3.00

The polyvinyl alcohol is dissolved in water, the re maining componentsof the mixture, with the exception of the propellant, are distributed inthe polyvinyl alcohol solution with the aid of a suitable apparatus. Themixture is treated with iso-butane in a pressure container. A readilysprayable preparation is obtained having the same properties as inExample 1, however it gives a distinctive White effect to textiles whichare sprayed and then hot pressed.

EXAMPLE 3 Parts Polyvinyl acetate-dispersion 50% 4.0 Dibutyldiethyleneglycol ether 1 1.0 Glycerine 0.5 Dichlorobenzoxazolone 0.5Water 84.0 Dichlorodifiuoromethane 4.0 Dichlorotetrafluorethane 6.0

1 (This compound is of the formula C4H0OCH2CH2O-CH2-CH2OC4H9 it iscommercially available as dlbutylcarbitol.)

The polyvinyl acetate-dispersion is diluted in water, the the remainingcomponents of the mixture, with the exception of the propellant, areadded to this dilution and homogenized with a suitable apparatus. Thismixture is mixed in a pressure container with the dichlorofiuoromethaneand the dichlorotetrafluorethane. The finished mixture has equally goodsprayability as that mentioned in Example 1: The fabric sprayedtherewith and then hot pressed has a good starch effect, which fabricpossesses as a result of the dichlorobenzoxazolone content excellentfungistatic and bacteristatic properties.

EXAMPLE 4 Parts Polyvinyl alcohol 5.00 Diethyleneglycol dibutyl ether1.00 Propyleneglycol a 1.50 Bis[(tri-n-butyl)-tin]-oxide 1 0.052,2-disulphonic acid 0.10 Pentachlorophenol, sodium salt 0.50 Water86.85 Dichlorodifluoromethane 5.00

The sodium salt of 4,4-bis(Z-m sulphani1ino-4-dlethano1-amino-1,3,5-triazin-6-yl) -d'iamino-stilbene.

The polyvinyl alcohol is dissolved in water, the remaining components ofthe mixture, with the exception of the propellant, are added anddistributed with the aid of a suitable apparatus. The mixture is treatedin a pressure vessel with the dichlorodifluoromethane. A readilysprayable three-phase aerosol is obtained. Sprayed onto cotton, thepreparation gives a soil-repellent finish after hot pressing With a goodwhite effect and also with a fungistatic and bacteristatic effect. 1part of ethyleneglycol monobutyl ether may be used in this instance asspray improving agent instead of the diether employed above.

EXAMPLE 5 Parts Starch derivative soluble in hot water 5.0

Diethyleneglycol-mono-n-hexyl ether (HLB value below 6) 1.5Propyleneglycol 1.0 Lavender oil 0.3

Water 72.2 Propane/butane (20:80) 20.0

The hot water soluble starch derivative is dissolved in hot water, theremaining components of the mixture, apart from the propellant, areadded to the starch solution and homogenized in a suitable apparatus.The mixture is treated with propane/butane (20:80) in a pressurecontainer. This preparation may be readily sprayed; sprayed on cotton,it produces after hot pressing an excellent starch effect.

We claim:

1. In a system comprising a pressure vessel and a sprayable mixturecontained in said vessel under pressure, which mixture consistsessentially of an aqueous phase to be sprayed, a liquefied organicpropellant phase and the gas phase of the propellant, the improvementconsisting in combination, in that (i) said aqueous phase consistsessentially of (a) a water-soluble or water-dispersible textilefinishing agent in an amount of from about 0.5 to 20% by weightcalculated on the total weight of said mixture,

(b) water in an amount of from 50% to about 93% by weight calculated onthe total weight of said mixture, said textile finishing agent beingdissolved or dispersed in said water; said aqueous phase and saidliquefied propellant phase not being emulsified with each other butbeing separated from each other forming a common interface; and

(ii) said mixture further contains a spray improving agent selected froma monoether and a diether of a glycol and an alkanol, said ether havingat least 6 and not more than 12 carbon atoms, said glycol being selectedfrom ethylene glycol, diethylene glycol, and propylene glycol, saidalkanol having from 4 to 6 carbon atoms, and said spray improving agenthaving an HLB value according to Griffin of maximally 6, in an amount offrom about 0.1 to 5% by weight calculated on the total weight of saidmixture, the major proportion of said spray improving agent beingpresent in said liquefied propellant phase, and a minor proportion ofsaid spray improving agent being present in said aqueous phase; and

(iii) said mixture is substantially free from monohydric alkanol of from1 to 5 carbon atoms.

2. The improvement described in claim 1, wherein said textile finishingagent is selected from water-soluble and Water-dispersible natural andmodified starch, polyvinyl alcohol, polyvinyl acetate, polystyrene resinand polyacrylic resin.

3. The improvement described in claim 1, wherein said spray improvingagent is mono-alkyl or di-alkyl ether of monoethylene glycol ordi-ethylene glycol, wherein alkyl has from 4 to 6 carbon atoms.

4. The improvement as described in claim 1, wherein said mixture furthercontains not more than 5% Of an optical Whitening agent derived fromstilbene, triazole or benzimidazole.

5. The improvement as described in claim 1, wherein said mixture furthercontains not more than 5% of an antimicrobially active substance.

6. The improvement as described in claim 2, wherein said textilefinishing agent consists of 0.5 to 10% by weight of a natural starchsoluble in water.

7. The improvement as described in claim 2, wherein said textilefinishing agent consists of 0.5 to 20% by weight of a modified starchderivative soluble in water.

8. The improvement as described in claim 1, wherein said spray improvingagent is diethyleneglycol mono-nhexyl ether.

9. The improvement as described in claim 1, wherein said spray improvingagent is diethyleneglycol di-butyl ether.

10. The improvement as described in claim 1, wherein said sprayimproving agent is ethyleneglycol di-butyl ether.

11. The improvement as described in claim 1, wherein said sprayimproving agent is ethyleneglycol mono-nhexyl ether.

12. The improvement described in claim 2 wherein said textile finishingagent is polyvinyl alcohol.

13. The improvement described in claim 2 wherein said textile finishingagent is polyvinyl acetate.

References Cited UNITED STATES PATENTS 8 3,402,056 9/1968 Ehrmantraus252305 3,419,658 12/1968 Sanders 252305 OTHER REFERENCES Griffin I,Society of Cosmetic Chemist Journal, vol. I, 5 December 1949, pp.311-321.

Grifiin II, Society of Cosmetic Chemist Journal, Vol, V, December 1954,pp. 249-256.

B06 252-305 Clapp 252 305 10 DONALD J. ARNOLD, Prlmary Examiner Curtinet al. 106- 13 A. H. KOECKERT, Assistant Examiner Klausner 252305 Sessoet a1. 167-39 US. Cl. X.R.

Read 106-15, 203, 213; 117-1395

